Whey protein retarder

ABSTRACT

A method and composition is provided using whey protein as a retarder in a cementing composition for use in cementing operations in a subterranean zone penetrated by a well bore.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Divisional of Ser. No. 10/026,027, filed Dec. 12,2001, now U.S. Pat. No. 6,591,909.

BACKGROUND

The present embodiment relates generally to a retarder for delayingsetting of a cementing composition in a subterranean zone penetrated bya well bore.

In the drilling and completion of an oil or gas well, a cementingcomposition is often introduced in the well bore for cementing pipestrings. In this process, known as “primary cementing,” a cementingcomposition is pumped into the annular space between the walls of thewell bore and the pipe string. The cementing composition sets in theannular space, supporting and positioning the pipe string, and forming asubstantially impermeable barrier which divides the well bore intosubterranean zones. After primary cementing, the undesirable migrationof fluids between zones is prevented. Likewise, cementing compositionsare often subsequently introduced into a subterranean zone for remedialoperations to recover circulation or to plug the well bore.

Regardless of the motivation for introducing the cementing compositioninto a subterranean zone (“cementing operations”), with relatively hotor deep well bores it is often necessary to add a component, known as a“retarder,” to the cementing composition to slow setting, therebyincreasing pumping time. A variety of factors affect the effectivenessof a retarder, including settling tendencies, environmentalfriendliness, and temperature range. For example, retarders are usuallyconsidered as those suitable for use at 100-200° F. and retarderssuitable for use at 200-300° F. These temperatures are based on downholetemperature measured while circulating fluid in the well bore, known asthe bottomhole circulating temperature (“BHCT”).

DESCRIPTION

The present embodiment provides for the use of whey protein as aretarder in a cementing composition for use in cementing operations in asubterranean zone penetrated by a well bore.

Whey is readily available as a by-product from the dairy industry, andcontains lactose, some salts, and a variety of proteins, includingbovine serum albumin “BSA” (molecular weight 66,000 Daltons),alpha-lactoglobulin (molecular weight 14,000 Daltons), andbeta-lactoglobulin (molecular weight 16,000 Daltons). The proteins maybe isolated from the whey, the isolated proteins being generallyreferred to as “whey protein.” Whey protein is readily available fromBorculo Whey Products, Borculo, Netherlands, under the trademark“PROXIME™.” Whey protein has designated whey protein concentrations(“WPC”) which vary from 10% -99%, and varying percentages of wheyprotein isolation (“WPI”) to indicate purity. The isoelectric pointoccurs at a pH of 5.4 approximately, and whey protein is water-solubleat all temperatures.

A cementing composition according to the present embodiment basicallycomprises a slurry including whey protein as a retarder, a cementitiousmaterial (“cement”), and sufficient water to form the slurry.

In one embodiment, the whey protein is used as a retarder in thecementing composition.

In an alternative embodiment, the whey protein is denatured byconventional denaturants, such as urea or sodium dodecyl sulfate(“SDS”), and then treated with formaldehyde or another crosslinker, andthen with tartaric acid, to form modified whey protein. The modifiedwhey protein is then used as a retarder in the cementing composition.

The cement may be Portland cement API Classes A-H (and preferably APIClass G cement), or may alternatively be slag cement, pozzolana cement,gypsum cement, high alumina content cement, or high alkalinity cement.The desired amount of cement is understandably dependent on thecementing operation.

As will be understood by those skilled in the art, the amount of wheyprotein retarder included in the cementing composition can varydepending upon the temperature and the particular pumping time requiredfor the cementing operation. Generally, the whey protein retarder ofeither of the above embodiments is present in the cementing compositionin an amount in the range of 0.1% to 4.0% by weight of the cement in thecomposition.

The water used to form the cementing composition slurry can be freshwater or salt water. The water is preferably included in the cementingcomposition in an amount in the range of 30% to 60% by weight of thecement.

As is readily comprehended by those skilled in the art, the cementingcomposition may contain additional components (“additives”) to achievedesired properties. For example, the cementing composition may containfine silica flour available from Halliburton Energy Services of Duncan,Okla., under the trademark “SSA-1™,” fluid loss additives available fromHalliburton Energy Services of Duncan, Okla., under the trademark“HALAD®-600LE+,” weighting additives available from Halliburton EnergyServices of Duncan, Okla., under the trademark “MICROMAX™,” and bondimproving/expanding additives available from Halliburton Energy Servicesof Duncan, Okla., under the trademark “MICROBOND HT™.”

The following examples are illustrative of the methods and compositionsdiscussed above.

EXAMPLE 1

Dyckerhoff Class G cement, sufficient water (44%) to form a slurry, andPROXIME™ whey protein powder in the percentages listed (by weight of thecement) in TABLE 1 were mixed to form slurries having a density of 1.91kg/L. The whey protein used had a WPC of 25-80% and WPI of >80%. Theorder of mixing was water, retarder, and then cement.

The slurries were incubated at the temperatures listed below, and settimes in hours:minutes are listed below in TABLE 1.

TABLE I Whey % 125° F. 140° F. 180° F. 215° F. 230° F. 240° F. 0.5 5:124:05  3:04 — — — 0.75 7:41 6:10  4:20 2:20 — — 1.0 9:36 8:10  6:12 3:19— — 1.5 — — 10:20 4:09 2:23 2:09 2.0 — — — 4:49 — 2:49 3.0 — — — — 2:52— 3.5 — — — — 3:31 —

As can be seen from the results listed in TABLE 1, increasingconcentration of whey protein increased the set time at all temperaturestested, thereby providing retardation.

EXAMPLE 2

Dyckerhoff Class G cement (100 kg), sufficient water (44%) to form aslurry, SSA-1™ silica flour (35%), and modified (denatured) whey protein(in L of 19% solution) in the percentages listed in TABLE 2 were mixedto form slurries having a density of 1.91 kg/L. The order of mixing waswater, additives, retarder, and then cement.

The 19% whey protein solution was formed with 30 grams of PROXIME™ wheyprotein powder dissolved in 120 mL of water. The whey protein used had aWPC of 25-80% and WPI of >80%. The amount of denaturant (urea) used was3.3% by weight of the whey protein. With the exception of the results inthe third results column in TABLE 2, the amount of formaldehyde used was6.6% by weight of the whey protein. The slurry in the third resultscolumn contained no formaldehyde, but was otherwise identical to theother slurries. The amount of tartaric acid used was 25% by weight ofthe whey protein, the tartaric acid is available from Halliburton EnergyServices of Duncan, Okla., under the trademark “HR®-25.” The slurrieswere incubated at the temperatures listed below in TABLE 2, andthickening times (TT) for reaching viscosities of 70 BC and 100 BC arelisted, as well as the respective rheologies.

TABLE 2 240° F. 275° F. 300° F. 300° F. 330° F. Modified Whey 10 Protein10 10 (No 10 14 (19% solution, in formaldehyde) L/100 kg cement) TT at70 BC 10:06 5:36 0:22 2:13 4:04 TT at 100 BC 10:06 5:37 — 2:14 4:09Rheology 270-197-109 300-210-113 95-66-34 132-92-46 151-100-57300-200-100 Rheology 69-37-12-10 72-38-13-11 21-10-2-1 23-13-4-332-18-5-4 60-30-6-3

As can be seen from the results listed in TABLE 2, modified whey proteinprovides retardation at increased temperatures when crosslinked.

EXAMPLE 3

To form a cementing composition of a typical high temperature North Seaslurry design, Dyckerhoff Class G cement (100%), sufficient fresh water(4.51 gps) to form a slurry, SSA-1™ silica flour (35%),HALAD®-600LE+fluid loss additive (0.8 gps), MICROMAX™ weighting additive(20%), and MICROBOND HT™ bond improving/expanding additive (4.0%) weremixed to form slurries having a density of 16.81 lb/gal when mixed withthe following. The order of mixing was water, additives, retarder, andthen cement.

The composition listed in the first results column of TABLE 3 had 0.2%of a suspension additive to prevent settling, available from HalliburtonEnergy Services of Duncan, Okla., under the trademark “SA-533™,” and 0.6gps of a synthetic retarder, available from Halliburton Energy Servicesof Duncan, Okla., under the trademark “SCR-500L™.”

The compositions listed in the second, third, and fourth results columnof TABLE 3 had modified (denatured) whey protein (19% solution) in thepercentages listed in TABLE 3. The 19% whey protein solution was formedwith 30 grams of PROXIME™ whey protein powder dissolved in 120 mL ofwater. The whey protein used had a WPC of 25-80% and WPI of >80%. Theamount of denaturant (urea) used was 3.3% by weight of the whey protein.The amount of formaldehyde used was 6.6% by weight of the whey protein.The amount of tartaric acid used was 25% by weight of the whey protein.

The slurries were incubated at the temperatures listed below in TABLE 3,and thickening times (TT) for reaching viscosities of 30 BC, 70 BC, and100 BC are listed, as well as the respective rheologies.

TABLE 3 Synthetic retarder 311° F. 311° F 311° F. 375° F. Modified — 1.5gps 1.5 gps 0.95 gps Whey Protein (19% solution) TT at 30 BC — 7:02 7:021:39 TT at 70 BC 1:36 7:02 7:04 1:41 TT at 100 BC 1:38 7:03 7:04 1:43Rheology after mix 180-126-65 190-138-75 — 139-94-48 300-200-100 (195°F.) (195° F.) Rheology after mix 40-22-6-4 47-26-6-4 — 30-15-3-260-30-6-3 (195° F.) (195° F.)

As can be seen from the results listed in TABLE 3, modified whey proteinprovides retardation at increased temperatures. No gellation problemswere observed for the modified whey protein cementing compositions. Thesynthetic retarder cementing composition had a gellation problem, inthat it displayed too short a thickening time.

Although only a few exemplary embodiments of this invention have beendescribed in detail above, those skilled in the art will readilyappreciate that many other modifications are possible in the exemplaryembodiments without materially departing from the novel teachings andadvantages of this invention. Accordingly, all such modifications areintended to be included within the scope of this invention as defined inthe following claims.

What is claimed is:
 1. A cement composition comprising: cement;sufficient water to form a slurry; and sufficient whey protein to retardthe cement composition.
 2. The composition of claim 1 wherein the wheyprotein is present in a range of from 0.1% to 4.0% by weight of cementin the composition.
 3. The composition of claim 1 wherein the wheyprotein comprises bovine serum albumin, alpha-lactoglobulin, andbeta-lactoglobulin.
 4. The composition of claim 1 wherein the wheyprotein has been denatured and crosslinked.
 5. The composition of claim4 wherein the whey protein is further treated with tartaric acid.
 6. Thecomposition of claim 1 wherein the cement is Portland cement, slagcement, pozzolana cement, gypsum cement, high alumina content cement, orhigh alkalinity cement.
 7. The composition of claim 1 wherein the wateris fresh water or salt water.
 8. The composition of claim 1 wherein thewater is present in the cementing composition in an amount in the rangeof 30% to 60% by weight of the cement in the cementing composition.
 9. Acement composition comprising: cement; sufficient water to form aslurry, wherein the water is selected from the group consisting of freshwater and salt water; and whey protein present in a range of from 0.1%to 4.0% by weight of cement in the composition.
 10. The composition ofclaim 9 wherein the whey protein comprises bovine serum albumin,alpha-lactoglobulin, and beta-lactoglobulin.
 11. The composition ofclaim 9 wherein the whey protein has been denatured and crosslinked. 12.The composition of claim 11 wherein the whey protein is further treatedwith tartaric acid.
 13. The composition of claim 9 wherein the cement isPortland cement, slag cement, pozzolana cement, gypsum cement, highalumina content cement, or high alkalinity cement.
 14. The compositionof claim 9 wherein the water is present in the cementing composition inan amount in the range of 30% to 60% by weight of the cement in thecementing composition.
 15. A cement composition comprising: cement;sufficient water to form a slurry, wherein the water is selected fromthe group consisting of fresh water and salt water; and whey proteincomprising bovine serum albumin, alpha-lactoglobulin, andbeta-lactoglobulin.
 16. The composition of claim 15 wherein the wheyprotein has been denatured and crosslinked.
 17. The composition of claim16 wherein the whey protein is further treated with tartaric acid. 18.The composition of claim 15 wherein the cement is Portland cement, slagcement, pozzolana cement, gypsum cement, high alumina content cement, orhigh alkalinity cement.
 19. The composition of claim 15 wherein thewater is present in the cementing composition in an amount in the rangeof 30% to 60% by weight of the cement in the cementing composition. 20.A cement composition comprising: cement selected from the groupconsisting of Portland cement, slag cement, pozzolana cement, gypsumcement, high alumina content cement, or high alkalinity cement; waterselected from the group consisting of fresh water and salt water presentin the composition in an amount in the range of from 30% to 60% byweight of the cement in the composition; and whey protein comprisingbovine serum albumin, alpha-lactoglobulin, and beta-lactoglobulinpresent in a range of from 0.1% to 4.0% by weight of cement in thecomposition.
 21. The composition of claim 20 wherein the whey proteinhas been denatured and crosslinked.
 22. The composition of claim 21wherein the whey protein is further treated with tartaric acid.
 23. Acement composition comprising: cement; water selected from the groupconsisting of fresh water and salt water, and present in an amountsufficient to form a slurry; and denatured and crosslinked whey proteinin an amount sufficient to retard the cement composition.
 24. Thecomposition of claim 23 wherein the whey protein is present in a rangeof from 0.1% to 4.0% by weight of cement in the composition.
 25. Thecomposition of claim 23 wherein the whey protein comprises bovine serumalbumin, alpha-lactoglobulin, and beta-lactoglobulin.
 26. Thecomposition of claim 23 wherein the whey protein is further treated withtartaric acid.
 27. The composition of claim 23 wherein the cement isPortland cement, slag cement, pozzolana cement, gypsum cement, highalumina content cement, or high alkalinity cement.
 28. The compositionof claim 23 wherein the water is present in the cementing composition inan amount in the range of 30% to 60% by weight of the cement in thecementing composition.